CN1219804C - Processes for producing hydrocarbon/phenol resin and producing epoxy resin - Google Patents
Processes for producing hydrocarbon/phenol resin and producing epoxy resin Download PDFInfo
- Publication number
- CN1219804C CN1219804C CNB008007306A CN00800730A CN1219804C CN 1219804 C CN1219804 C CN 1219804C CN B008007306 A CNB008007306 A CN B008007306A CN 00800730 A CN00800730 A CN 00800730A CN 1219804 C CN1219804 C CN 1219804C
- Authority
- CN
- China
- Prior art keywords
- hydrocarbon
- reaction
- phenol resin
- phenol
- phenolic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Epoxy Resins (AREA)
Abstract
A process for efficiently producing a hydrocarbon/phenol resin having a satisfactory hue through reaction of a phenol with an unsaturated cyclic hydrocarbon having two or more carbon-carbon double bonds in the presence of an acid catalyst, which comprises (1) a step in which the molar fraction of ether type reaction products to all the reaction products is regulated to at least 0.1 and (2) a step in which the ether type reaction products yielded by the progress of the reaction is substantially eliminated. The hydrocarbon/phenol resin thus obtained is reacted with an epihalohydrin in the presence of a base catalyst to obtain an epoxy resin having an excellent hue.
Description
Technical field
The present invention relates to a kind ofly derive and the hydrocarbon-phenol resin (for example DCPD-phenolic resin) that comes, excellent property such as wet fastness, thermotolerance, resistance to cracking and tone are good and with its manufacture method as the Resins, epoxy of raw material by the unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds (for example dicyclopentadiene (DCPD) etc.) and phenolic compound (for example phenol etc.).
In more detail, because excellent propertys such as thermotolerance, wet fastness, resistance to cracking, as electrically insulating material, particularly with resin of great use as semiconductor sealing material use resin and laminated wood, in addition, since excellent color tone, the phenol resins that the outward appearance of forming composition and mark etc. are good and the manufacture method of Resins, epoxy.
Background technology
Past, the manufacture method of known DCPD-phenolic resin is, in the presence of acid catalysts such as friedel-crafts such as boron trifluoride complex (Friedel-Crafts) catalyzer or ion exchange resin, phenolic compound and DCPD are made by contact reacts.
But the painted of the DCPD-phenol resins in past significantly presents chocolate, and therefore, the non-constant of the outward appearance of moulded products exists the problem that presents very dark chocolate too with its Resins, epoxy as raw material and epoxyhalopropane reaction acquisition.If as sealing material, then because labeling properties is poor, operating efficiency is extremely low with painted Resins, epoxy.
Therefore, the spy opens in flat 7-252349 communique etc. and discloses a kind of like this method: as catalyzer, DCPD and phenol are reacted at low temperatures for a long time boron trifluoride-phenol complexes, obtain painted few resin thus.But,, can not say that one reduces the painted of hydrocarbon-phenol resin surely even adopt this method.Further, owing to must react for a long time, the total ascent time surpasses 20 hours, and existing needs a lot of labor forces, the problem of aspects such as manufacturing cost increase.
Problem of the present invention is, provide a kind of phenolic compound and unsaturated cyclic hydrocarbon of making in the presence of acid catalyst, to react with 2 above carbon-to-carbon double bonds, high-level efficiency and make the method for the good hydrocarbon-phenol resin of tone at short notice, further, also provide a kind of by make above-mentioned phenol resins in the presence of alkaline catalysts with epoxyhalopropane reaction, the Resins, epoxy of same less painted and excellent color tone.
Disclosure of an invention
Present inventors are in order to solve above-mentioned problem, carried out deep research repeatedly, the ether type resultant of by-product in the method that is conceived in the presence of the friedel-crafts acid catalyst, make phenolic compound and unsaturated cyclic hydrocarbon reaction make phenol resins, the manufacture method of can be with high-level efficiency and producing the good hydrocarbon-phenol resin of tone has at short notice finally been finished in constrained optimization when reacting.
Promptly, the 1st invention of the present invention relates to a kind of manufacture method of hydrocarbon-phenol resin, it is characterized in that, adopts the operation that comprises following (1) and (2), in the presence of acid catalyst, carry out phenolic compound and reaction with unsaturated cyclic hydrocarbon of 2 above carbon-to-carbon double bonds:
(1) make ether type resultant in the total reaction resultant shared molar percentage in the operation more than 0.1;
(2) operation that in fact the middle ether type resultant that generates of the operation (1) of carrying out above-mentioned reaction is eliminated.
The 2nd invention of the present invention relates to a kind of manufacture method of hydrocarbon-phenol resin, it is characterized in that, the operation of employing comprises following (1) and (2), in the presence of acid catalyst, carry out phenolic compound and reaction with unsaturated cyclic hydrocarbon of 2 above carbon-to-carbon double bonds:
(1) in the temperature range of the comparatively high temps to 90 from the fusing point of phenolic compound and 50 ℃ ℃, Yi Bian on one side in phenolic compound, add the operation that the unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds makes its reaction one by one or continuously;
(2) after the interpolation of above-mentioned unsaturated cyclic hydrocarbon finishes, temperature is brought up to more than 110 ℃ the operation that it is reacted.
The 3rd invention of the present invention relates to a kind of manufacture method of hydrocarbon-phenol resin, it is characterized in that, in the hydrocarbon-phenol resin that generates in the of the present invention the 1st or the 2nd invention, with respect to the position of substitution of phenolic hydroxyl group, the substitute proportion of ortho position/contraposition is more than 2.0 in phenolic compound for the unsaturated cyclic hydrocarbon.
The 4th invention of the present invention relates to a kind of manufacture method of hydrocarbon-phenol resin, it is characterized in that, in the of the present invention the 1st or the 2nd invention, after reaction finishes, reclaims unreacted phenolic compound after making catalyst deactivation.
The 5th invention of the present invention relates to a kind of manufacture method of hydrocarbon-phenol resin, it is characterized in that, in the of the present invention the 1st or the 2nd invention, phenolic compound is a phenol, and the unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds is a dicyclopentadiene.
The 6th invention of the present invention relates to a kind of manufacture method of Resins, epoxy, it is characterized in that, in the presence of alkaline catalysts, after the hydrocarbon-phenol resin that the manufacture method of the present invention the 1st or the 2nd invention is obtained reacts with epoxyhalopropane, remove catalyst residue, remove unreacted epoxyhalopropane.
The method according to this invention can be passed through the reaction of high-level efficiency, short period of time, obtains the good hydrocarbon-phenol resin of tone, for example the DCPD-phenol resins.
In addition, the hydrocarbon-phenol resin that obtains like this after epoxypropylization in the presence of the alkaline catalysts, is removed catalyst residue, unreacted epoxyhalopropane is removed in distillation, makes with extra care, and the curing characteristics of thus obtained Resins, epoxy is good, and tone is good.
Below, illustrate in greater detail the present invention.
The manufacture method of the hydrocarbon-phenol resin among the present invention is as follows.
That is, in the presence of acid catalyst, phenolic compound and the unsaturated hydrocarbons with 2 above carbon-to-carbon double bonds are reacted.
Among the present invention, the unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds that uses as the hydrocarbon-phenol resin material composition can be a crosslinking structure.The number of carbon-to-carbon double bond is as long as have more than 2 in 1 molecule, preferably below 4.
As concrete unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds, can enumerate dicyclopentadiene, 4 vinyl cyclohexene, 5-vinyl norbornene-2-alkene, 3a, 4,7,7a-tetrahydroindene, α-Pai Xi, limonene etc.They also can mix use.Consider preferred especially dicyclopentadiene from the good viewpoint of thermotolerance, wet fastness and mechanical characteristics of the resin that obtains.
In addition, the phenolic compound that uses among the present invention also can be defined as the aromatics of hydroxyl, so long as have at least a hydroxyl to be bonded directly to aromatics on the aromatic ring, just there is no particular limitation.As aromatic ring, can enumerate the naphthalene nucleus of phenyl ring, condensed type etc.
Therefore, as the object lesson of the phenolic compound that uses among the present invention, can enumerate phenol, ortho-cresol, meta-cresol, p-cresol, phlorol, m-ethylphenol, p-ethyl phenol, o-propylphenol, a propylphenol, n-propyl phenol, to sec-butyl phenol, p-tert-butylphenol, to monohydric phenol compounds such as cyclohexylphenol, para-chlorophenol, adjacent bromophenol, a bromophenol, p bromophenol, naphthyl alcohol, 2-Naphthols; Resorcinol, pyrocatechol, Resorcinol, 2,2-two (4 '-hydroxyphenyl) propane; Dihydric phenols compounds such as two (hydroxyphenyl) methane, two (hydroxyl naphthyl) methane, tetramethyl biphenyl base bis-phenol, xenyl bis-phenol; Trihydric phenol compounds such as three (hydroxyphenyl) methane and their mixture etc.Especially, consider preferred phenol, ortho-cresol, meta-cresol, naphthyl alcohol, 2-Naphthol and 2,2-two (4 '-hydroxyphenyl) propane etc. from the viewpoint of economy and manufacturing easily.They also can mix use.
In the reaction of unsaturated cyclic hydrocarbon and phenolic compound, the blending ratio of the two can be selected aptly according to the molecular weight and the melt viscosity of the hydrocarbon-phenol resin that obtains.But the mol ratio that preferably makes phenolic compound/unsaturated cyclic hydrocarbon usually is 1～20 scope.Especially, the melt viscosity that obtains resin in order to make reduces, and the mol ratio of phenolic compound/unsaturated cyclic hydrocarbon is preferably in 5～15 scope.If the hydrocarbon-phenol resin epoxidation that melt viscosity is low just can obtain the same low Resins, epoxy of melt viscosity, they are used under the occasion of semiconductor-encapsulating material etc., filler is high fills owing to can make, linear expansivity is reduced, and, all be preferred because water tolerance improves.Under the few occasion of catalyst levels, the mol ratio that preferably makes phenolic compound/unsaturated cyclic hydrocarbon is 7～10.
As the acid catalyst that is used to make hydrocarbon-phenol resin, can enumerate Friedel-Crafts catalyst, especially, from viewpoint consideration active and that remove catalyzer easily, can use boron trifluoride, its complex compound catalyst, for example boron trifluoride-ether complexes, boron trifluoride-phenol complex compound, boron trifluoride-aquo complex, boron trifluoride-alcohol complex, boron trifluoride-amine complex or their mixture etc.Wherein more preferably boron trifluoride, boron trifluoride-phenol complex compound and boron trifluoride-ether complexes.
In the 1st invention of the present invention, the catalyst concn in the reaction system generally can be selected in the scope of 0.001～10 quality %.
Can use solvent in the manufacturing processed of hydrocarbon-phenol resin, the solvent of this occasion only otherwise hinder reaction just has no particular limits.As preferred solvent, can enumerate aromatic hydrocarbon compounds such as benzene,toluene,xylene etc.
The consumption of solvent for above-mentioned phenolic compound 100 mass parts, is preferably 20～300 mass parts.Should illustrate, when employed phenolic compound is superfluous with respect to the unsaturated cyclic hydrocarbon, there is no need to use other solvent.
In the 1st invention of the present invention, usually, temperature of reaction can be selected in the scope of fusing point～200 of phenolic compound ℃ aptly, and the reaction times can be selected in 10 minutes～100 hours scope aptly.
By phenolic compound and unsaturated cyclic hydrocarbon reaction are made under the occasion of hydrocarbon-phenol resin, except generating hydrocarbon-phenol resin, also may go out ether type resultant by by-product.This ether type resultant is that the unsaturated cyclic hydrocarbon adds on the phenolic hydroxyl group that phenolic compound has, and hydroxyl is transformed into ehter bond and the compound that forms, so its generation is not preferred.
Therefore, all be to study to suppress the method that this ether type resultant forms as far as possible usually, but among the present invention, adopt to make it generate the above method of certain proportion energetically.Adopt the result of this method to be, can be with high reaction efficiency, make resin at short notice, and can obtain the good resin of tone.
That is, in the operation (1) in the 1st invention of the present invention, make ether type resultant shared molar percentage in total resultant make phenolic compound and unsaturated cyclic hydrocarbon reaction more than 0.1 with 2 above carbon-to-carbon double bonds.Difference along with the interpolation order of reaction raw materials, reaction conditions etc., ether type resultant shared molar percentage in total resultant is reached more than 0.1, but among the present invention, in phenolic compound or unsaturated cyclic hydrocarbon or the two roughly during total overall reaction, the molar percentage of ether type resultant is adjusted to more than 0.1.
As mentioned above, importantly, make ether type resultant shared molar percentage in total resultant make phenolic compound and unsaturated cyclic hydrocarbon reaction more than 0.1 with 2 above carbon-to-carbon double bonds, under the occasion of the molar percentage less than 0.1 of ether type resultant, because the tonal difference of the resin that obtains is not preferred.
Ether type resultant shared molar percentage in total resultant does not have special higher limit, if but the amount of ether type resultant is too much, then the yield of purpose product hydrocarbon-phenol resin reduces, and over-burden to make the operation (2) of follow-up elimination ether type resultant in addition.Therefore, higher limit serves as suitable with 0.5 usually.
In order to adjust the ratio of ether type resultant, conditions such as selective reaction temperature, reaction times, catalyst concn aptly.In addition, because the water content in the reaction system etc. are also influential, therefore regulate water content aptly and react.If adopt method of the present invention, change under the occasion of conditions such as temperature of reaction, reaction times, catalyst concn according to for example change of device, raw material etc., if the ratio of ether type resultant as index, then can easily be carried out the setting of these conditions.
Should illustrate that the assay of ether type resultant adopts
13C-NMR carries out.As
13The condition determination of C-NMR, solvent uses CDCl
3, carry out according to the method for NNE (nuclear Overhauser effect decoupling method), can obtain
13The areal intensity of chemical shift 155～160ppm on the C-NMR spectrogram is divided by the value of each areal intensity sum of chemical shift 130～133ppm, 137～140ppm and 155～160ppm.
13The resonant frequency of C-NMR can be 400MHz for example.
Then, in the operation of the present invention (2), reaction is proceeded, in fact ether type resultant is eliminated.Usually in phenolic compound or unsaturated cyclic hydrocarbon or the two roughly after the complete reaction, in the scope in above-mentioned temperature of reaction and reaction times, in the presence of acid catalyst, continue heating and stir, in fact ether type resultant is eliminated.Usually the temperature that adopts is higher more than 20 ℃ than the temperature of reaction of operation (1), and is preferred high more than 30 ℃.Should illustrate, because making the reaction of the operation (1) of ether type resultant generation energetically carries out faster, the reaction of operation (2) is also preferably carried out under higher temperature, the result is, short from the total reaction times of reaction beginning, therefore can be, make the good hydrocarbon-phenol resin of tone in short time with high-level efficiency.Usually, in beginning to add up to 10 hours from reaction, can make the good resin of tone with the interior short period of time.
Herein, as preferably creating conditions of hydrocarbon-phenol resin, shown in the 2nd invention of the present invention, (1) in the presence of acid catalyst, in the temperature range of the comparatively high temps to 90 from the fusing point of phenolic compound and 50 ℃ ℃, in phenolic compound, add unsaturated cyclic hydrocarbon one by one or continuously with 2 above carbon-to-carbon double bonds, make its reaction after, (2) temperature of reaction is brought up to more than 110 ℃, further reacted.
That is, in phenolic compound, adding the operation (1) of unsaturated cyclic hydrocarbon one by one or continuously, in the temperature range of the comparatively high temps to 90 from the fusing point of phenolic compound and 50 ℃ ℃, react.Temperature of reaction surpasses under 90 ℃ the occasion, and the decomposition of unsaturated cyclic hydrocarbon (for example DCPD) might take place simultaneously, and in addition, the tone of the resin of acquisition reduces, and is not preferred therefore.The reaction times of operation (1) has no particular limits, and can select aptly in 10 minutes～60 hours scope usually.
In the range of reaction temperature in above-mentioned operation (1),, reaction is finished for phenolic compound or unsaturated cyclic hydrocarbon or for both sides' reaction raw materials.Owing to exist superfluous phenolic compound usually, therefore, in above-mentioned temperature of reaction, in fact make unsaturated cyclic hydrocarbon complete reaction.
Adopt above-mentioned method, can make ether type resultant shared molar percentage in total resultant make phenolic compound and unsaturated cyclic hydrocarbon reaction more than 0.1 with 2 above carbon-to-carbon double bonds.
Then, in operation (2), reaction is further carried out, so that in fact the ether type resultant that in a single day generates in the above-mentioned operation is eliminated.In order to reach this purpose, importantly temperature of reaction is brought up to the high temperature of temperature than operation (1), specifically, be more than 110 ℃, be preferably 120～170 ℃ scope.Especially, if under 140～150 ℃, react, then can be, obtain the good hydrocarbon-phenol resin of tone in short time with high-level efficiency.During 110 ℃ of the temperature of reaction deficiencies of operation (2), in case just need long time in fact the ether type resultant that generates is eliminated, therefore unfavorable economically, be not preferred.In addition, if temperature of reaction surpasses 170 ℃, then the tone of the resin of Huo Deing reduces, and the decomposition or the side reaction of catalyzer may take place, therefore preferably below 170 ℃.
As mentioned above, the ether type resultant that generates in the operation (1) is a by product, therefore, its final content is reduced.Generally, the molar percentage that makes ether type resultant account in the operation (2) total resultant reaches below 0.05, more preferably reaches 0.02 and react followingly.Reaction times has no particular limits, usually can 1～5 hour, particularly in 2～3 hours reaction times, in case in fact the ether type resultant that generates is eliminated.
Should illustrate,, can in above-mentioned 2 periods reaction times are aggregated in 10 hours with the interior short period of time, produce the good resin of tone usually if adopt method of the present invention.
In the manufacturing of hydrocarbon-phenol resin of the present invention, catalyst concn in the reaction system is influential to reaction path and the position of substitution of unsaturated cyclic hydrocarbon, therefore, be below the 1.00 quality % of total quality of phenolic compound, unsaturated cyclic hydrocarbon and catalyzer, be preferably 0.05～1.00 quality %.Specifically, for example in the reaction of phenol and dicyclopentadiene, acid catalyst uses under the occasion of boron trifluoride-phenol complexes, and the addition that makes catalyzer is that 1.00 quality % of the total quality of phenol, dicyclopentadiene and catalyzer react followingly.The catalyzer of this amount of surpassing can promote the tone of resin to reduce, and the decomposition reaction of resin takes place simultaneously, is not preferred therefore.
In addition, the water content in the reaction system has no particular limits, but by making moisture concentration below the 200ppm, more preferably below 100ppm, can correctly control the carrying out of reaction.Because phenolic compound has the structure of polar functionalities, contains moisture easily.As dewatering, can enumerate the method that for example under nitrogen gas stream, makes phenolic compound and organic solvent azeotropic etc., but, tend to take place moisture absorption owing to bleed when waiting processing in the reaction system inherence, therefore, must give one's full attention to during dehydration.Any occasion all must be from sampling in the system to confirm water content.In addition, unsaturated cyclic hydrocarbon etc. also must adopt ordinary method to carry out re-using after the processed.
Should illustrate, in the time of reaction, use usually in the inert gas replacement reactor, under this occasion, preferably become the laggard line replacement of enclosed system earlier.Under the occasion of in open system, reacting, react on one side also can in reactor, supply with rare gas element on one side.As rare gas element used herein, can enumerate nitrogen, argon gas etc.
Adjust the water content in the reaction system atmosphere like this, making the water content in the reaction system is to be important below the 100ppm.
The manufacture method of hydrocarbon-phenol resin of the present invention, as long as adopt above-mentioned condition to make phenolic compound and unsaturated cyclic hydrocarbon reaction, just there is no particular limitation for concrete reaction method, for example can enumerate following method.
That is, phenolic compound is added in the reactor with as required certain amount of organic solvent, then heat, remove organic solvent and moisture as azeotropic mixture.Reach the water content of defined in the affirmation system, for this reason, the liquid of extracting out usually in the system is measured.Then, in system, add quantitative acid catalyst, splash into the unsaturated cyclic hydrocarbon.Because the water content of unsaturated cyclic hydrocarbon also must be adjusted, and therefore, preferably measures its water content in advance and adopts ordinary method to dewater.
Among the present invention, adopt aforesaid method to make after the hydrocarbon-phenol resin, make catalyst deactivation, positively stopped reaction.For example, the reacting by heating mixture if do not make catalyst deactivation, reaction is further carried out, and along with the difference of occasion, can produce undesirable situation.
The method of inactivation has no particular limits, and the preferred method that adopts is to make the remaining quantity of boron in the hydrocarbon-phenol resin of final acquisition, fluorine isoiony impurity below 100ppm.In order to reach this purpose, preferably use deactivator, as deactivator, can use basic metal, alkaline-earth metal or their oxide compound, oxyhydroxide, carbonate etc., perhaps inorganic base such as ammonium hydroxide, ammonia can use hydrotalcite in addition.Hydrotalcite also can adsorbed ion impurity, therefore handles rapidly succinctly, and the remaining quantity of the ionic impurity after handling is also few, and therefore, for processing reaction liquid, the purpose that makes catalyst deactivation is particularly preferred.
After making acid catalyst inactivation and absorption with hydrotalcite etc., remove by filter the hydrotalcite that adsorbed acid catalyst etc., reclaim the reaction solution that does not in fact contain catalyst residue, then distill concentration of reaction solution, can obtain highly purified hydrocarbon-phenol resin thus.When filtering the time, adopt to add solvent or carry out the method for heat treated etc., can make filtering operability good.
Among the present invention, reclaim unreacted phenolic compound, can obtain purpose product hydrocarbon-phenol resin by from the filtrate of adopting aforesaid method to obtain, concentrating.
Adopt above-mentioned the inventive method in the hydrocarbon-phenol resin that generates, about the unsaturated cyclic hydrocarbon at the position of substitution with respect to the hydroxyl on the aromatic nucleus of phenol, the substitute proportion that can make ortho position/contraposition is more than 2.0, its result can obtain the good hydrocarbon-phenol resin of balance of resin properties such as color harmony solidified nature.
The mensuration of the substitute proportion of above-mentioned ortho position/contraposition (O/P ratio) is to adopt
13C-NMR carries out.During this was measured, solvent used CDCl
3, carry out, obtain according to NNE (nuclear Overhauser effect decoupling method method) method
13The areal intensity of chemical shift 130～133ppm on the C-NMR spectrogram is divided by the value of the areal intensity of chemical shift 137～140ppm.Should illustrate that resonant frequency can be 400MHz.
In addition, during the tone of the resin that obtains among the present invention is estimated, if use the method for employing Gardner (Gardner) standardized solution of stipulating among the known JIS-K-5400 of past, though be the evaluation method of solution tone, may not be consistent with the actual tone of solid state resin.And owing to estimate with the standard colour tone liquor ratio, mensuration person's determinating reference there are differences, and evaluation result often has skew.
To this, utilize the mensuration of carrying out in the absorbancy in visible UV field, skew is few, and is good with the dependency of actual tone, and therefore, tone evaluation method of the present invention adopts absorbance method.Below the tone evaluation assessment of absorbancy is adopted in explanation.
In this method, use resin is diluted in diluting soln in any solvent.As diluting solvent, in the whole field of visual ultraviolet, to absorb few being advisable, therefore, preferably use sturated aliphatic hydrocarbon, sturated aliphatic hydrocarbon ether etc., but consider special You Xuan diox and tetrahydrofuran (THF) etc. from the good viewpoint of dissolving resin.Measure the absorbancy of solution, judge tone thus at the 350nm place.That is, the hydrocarbon-phenol resin that the tone that obtains among the present invention is good, the absorbancy at the 350nm place has notable attribute, and this absorbancy is below 1.0, and it is good in fact to be equivalent to tone, preferably as the raw material of the Resins, epoxy in the subsequent reactions.
The hydrocarbon-phenol resin of Huo Deing like this except as the raw material of Resins, epoxy, can also be used as electrically insulating material, and particularly the curing agent for epoxy resin of using as semiconductor sealing material use or laminated wood of great use.Because excellent color tone, the outward appearance of moulded products and mark etc. are good, especially, are not subjected to the qualification of such use.
Below the method for the good Resins, epoxy of tone is made the hydrocarbon-phenol resin of above-mentioned acquisition in explanation as raw material.
That is, the Resins, epoxy that tone of the present invention is good can make hydrocarbon-phenol resin and the reaction of epoxyhalopropane class of adopting aforesaid method to obtain under alkaline catalysts, obtain through epoxypropylization.The epoxypropyl reaction adopts ordinary method to carry out.Specifically, can be in the presence of for example alkali such as sodium hydroxide, potassium hydroxide, usually 10～150 ℃, preferably under 30～80 ℃ temperature, make epoxypropyl reagent reacts such as above-mentioned hydrocarbon-phenol resin and epoxy chloropropane, epoxy bromopropane after, obtain through washing, drying.
At this moment, the consumption of epoxypropyl reagent is preferably 2～20 times of molar equivalents of hydrocarbon-phenol resin, is preferably 3～7 times of molar equivalents especially.In addition, during reaction, under reduced pressure, remove by epoxypropyl reagent and water component distillation and to anhydrate, reaction is carried out quickly.
In addition, in field of electronic materials, use under the occasion of Resins, epoxy of the present invention, must in washing step, the sodium-chlor of by-product in the above-mentioned epoxypropylization be removed fully in advance.At this moment, also can reclaim epoxypropyl reagent, behind the concentrated reaction solution, enriched material is dissolved in the solvent, wash by distillation.As solvent, preferable methyl isobutyl ketone, pimelinketone, benzene, ethylene glycol butyl ether etc.To concentrate through the enriched material heating of washing, can make Resins, epoxy.
Epoxy equivalent (weight) in the above-mentioned Resins, epoxy (the resin gram number that contains 1 gram equivalent of epoxy group(ing)) is generally 200～500, is preferably 250～450.Epoxy equivalent (weight) surpasses under 500 the occasion, and cross-linking density reduces, and is not preferred therefore.
The Resins, epoxy of Huo Deing is compared as the Resins, epoxy of raw material with the hydrocarbon-phenol resin that the past method of employing obtains like this, excellent color tone, and the outward appearance of moulded products and mark etc. are good.Should illustrate that adopt absorbancy that aforesaid method measures 0.8 below, the tone of reality is also good, is preferred.
Further, the Resins, epoxy of acquisition, the result of employing gel permeation chromatography, the content of simple function body is few, and is below 0.5 quality %, most of below 0.1 quality % usually.Therefore, curing characteristics is also good.
Because the excellent color tone of above-mentioned Resins, epoxy, so the outward appearance of moulded products and mark etc. are good.Therefore, as electrically insulating material, particularly as encapsulating semiconductor with or the composition epoxy resin raw material used of laminated wood be of great use, especially, be not subjected to the qualification of these purposes, also be useful at aspects such as powder coating, brake pad.
The preferred plan that carries out an invention
Below illustrate in greater detail the present invention with embodiment and comparative example.
The characteristic of the hydrocarbon-phenol resin in following examples and the comparative example adopts following method to measure.
(1) substitute proportion of ortho position/contraposition (O/P ratio)
Use 10 quality %CDCl of hydrocarbon-phenol resin
3Solution is used
13C-NMR (fourier transformation type nuclear magnetic resonance device; Trade(brand)name: JNM-400, NEC (strain) system; Resonant frequency 400MHz) measures.
If A
1The areal intensity of=chemical shift 130～133ppm, A
2The areal intensity of=chemical shift 137～140ppm, then the O/P ratio can be obtained by following formula.
O/P ratio=A
1/ A
2
(2) ether type resultant content
Use 10 quality %CDCl of hydrocarbon-phenol resin
3, use
13C-NMR (fourier transformation type nuclear magnetic resonance device; Trade(brand)name: JNM-400, NEC (strain) system) measure.
If A
1The areal intensity of=chemical shift 130～133ppm, A
2The areal intensity of=chemical shift 137～140ppm, A
3The areal intensity of=chemical shift 155～160ppm, then ether type resultant content (molar percentage) can be obtained by following formula.
Ether type resultant content=A
3/ (A
1+ A
2+ A
3)
(3) UV visual absorbancy
Use 2 quality % dioxane solutions of hydrocarbon-phenol resin, measure by following condition.
Analytical instrument: UV visual spectrophotometer (trade(brand)name: Ubest-50 type, Japanese beam split industry (strain) system)
Cell: quartzy system, the wide 4mm of optical path length 10mm * light path
(4) Gardner's chromatic number
Gardner's standardized solution of stipulating among Gardner's chromatic number of 50% dioxane solution of hydrocarbon-phenol resin and the JIS-K-5400 compared decide.
(5) the simple function body burden of Resins, epoxy
Use WATERS corporate system Chromatography manager Millenium 2000 and differential refractive spectrophotometer (trade(brand)name: WATERS 410), adopt gel permeation chromatography (being designated hereinafter simply as " GPC ") to measure.
Embodiment 1
(manufacturing of hydrocarbon-phenol resin-1)
Add phenol and toluene in reactor, be heated to 160 ℃, make toluene and water azeotropic, toluene is removed in distillation simultaneously.Phenol amount in the system after the dehydration is 750g.Take a sample aptly, the water content of phenol is below 100ppm in the affirmation system.Then, add boron trifluoride-phenol complexes 2.3g, behind the uniform mixing, on one side the liquid temperature is remained on 70 ℃, in 1 hour, slowly splash into dicyclopentadiene 150g on one side.After splashing into end, be warmed up to 140 ℃, restir 3 hours.
The content of the ether type resultant after mensuration splashes into is learnt, is 0.43.
Should illustrate that dicyclopentadiene etc. are measured in addition, confirm that water content is below 100ppm.In addition, also the water content of assaying reaction system aptly confirms that its water content is below 100ppm.
After reaction finishes, stop to stir, reaction solution be cooled to 70 ℃, add hydrotalcite (trade(brand)name: キ ョ-ワ-De 1000, consonance chemical industry (strain) system) 5.5g, make catalyst deactivation after, filtering reacting liquid.The filtrate decompression distillation that obtains is concentrated, obtain hydrocarbon-phenol resin 326g.
The softening temperature of the hydrocarbon-phenol resin that obtains is 93.0 ℃, and phenolic hydroxyl group equivalent (the resin gram number that contains 1 gram equivalent of hydroxyl) is 170.
With
13The O/P ratio that C-NMR measures is 2.7, and ether type resultant content is below 0.01.
In addition, measure the absorbancy of resin solution and learn that the absorbancy of 350nm is 0.983, Gardner's chromatic number is 16～17.
The results are shown in the table 1.
Embodiment 2
(manufacturing of Resins, epoxy-1)
In 3 liters of 4 mouthfuls of flasks that have stirrer, reflux exchanger and thermometer, the hydrocarbon-phenol resin 170g and the epoxy chloropropane 400g that add the method manufacturing of adopting embodiment 1, make its dissolving and stirring then, the pressure in the reaction system is adjusted to 150mmHg (200hPa), be warmed up to 68 ℃.Adding concentration continuously in this system on one side is the aqueous sodium hydroxide solution 100g of 48 quality %, Yi Bian carry out 3.5 hours reaction.The water that reaction generates and the water of aqueous sodium hydroxide solution as water-epoxy chloropropane azeotropic mixture, are discharged to outside the reaction system continuously by refluxing.Reaction makes reaction system return normal pressure after finishing, and is warmed up to 110 ℃, removes the water of reaction system fully.Under normal pressure, the epoxy chloropropane distillation of surplus is removed, under the decompression of 15mmHg (20hPa), under 140 ℃, distill again.
In the mixture of resin that generates and sodium-chlor, add the aqueous sodium hydroxide solution 36g of methyl iso-butyl ketone (MIBK) 300g and 10 quality %, under 85 ℃ temperature, carry out 1.5 hours reaction.After reaction finishes, add methyl iso-butyl ketone (MIBK) 750g and water 300g, the sodium chloride aqueous solution separatory of lower floor is removed.Then, add 150g water in the methyl iso-butyl ketone (MIBK) liquid layer, washing with the phosphoric acid neutralization, behind the separation water layer, is used the 800g water washing again, separates water layer.The separation property of oil reservoir and water layer is good, reclaims inorganic salt quantitatively.Distillation methyl iso-butyl ketone (MIBK) liquid layer under normal pressure then carries out underpressure distillation under 5mmHg (6.7hPa), 140 ℃, obtain the Resins, epoxy of 220g.The epoxy equivalent (weight) of this Resins, epoxy is 261.In addition, the content of the simple function body of employing GPC method mensuration is below 0.1 quality %.
In addition, measure the absorbancy of 2% dioxane solution of resin and learn that the absorbancy of 350nm is 0.741, Gardner's value is 14～15.
The results are shown in the table 1.
Embodiment 3
(manufacturing of hydrocarbon-phenol resin-2)
In reactor, add phenol and toluene, carry out azeotropic dehydration similarly to Example 1.Phenol amount after the dehydration is 780g.Then, add boron trifluoride-phenol complexes 1.7g, splash into dicyclopentadiene 120g, operate similarly to Example 1.
Ether type resultant containing ratio after mensuration splashes into is learnt, is 0.31.
Should illustrate that dicyclopentadiene etc. are measured in addition, confirm that water content is below 100ppm.In addition, also the water content of assaying reaction system is aptly confirmed below 100ppm.
After reaction finishes, stop to stir, reaction solution be cooled to 70 ℃, add the 4.0g hydrotalcite, make catalyst deactivation after, filtering reacting liquid.The filtrate decompression distillation that obtains is concentrated, obtain hydrocarbon-phenol resin 258g.
The softening temperature of this hydrocarbon-phenol resin is 90.0 ℃, measures hydroxyl equivalent and learns, and be 169.Adopt
13The O/P ratio that C-NMR measures is 2.6, and ether type resultant containing ratio is below 0.01.
In addition, the absorbancy of the 350nm of 2% dioxane solution of mensuration resin is learnt, is 0.851, and Gardner's chromatic number is 13～14.
The results are shown in the table 1.
Embodiment 4
(manufacturing of Resins, epoxy-2)
In using embodiment 3, the synthetic hydrocarbon-phenol resin 169g, operate similarly to Example 2, obtain 182g Resins, epoxy.The epoxy equivalent (weight) of this Resins, epoxy is 256.In addition, the amount of the simple function body of employing GPC method mensuration is below 0.1 quality %.
In addition, measure the absorbancy of resin and learn that the absorbancy of 350nm is 0.710, Gardner's chromatic number is 11～12.
The results are shown in the table 1.
Comparative example 1
(manufacturing of hydrocarbon-phenol resin-3)
Add phenol and toluene in reactor, be heated to 160 ℃, make toluene and water azeotropic, toluene is removed in distillation simultaneously.Phenol amount in the system after the dehydration is 750g.Take a sample aptly, the water content of phenol is below 100ppm in the affirmation system.Then, after adding boron trifluoride-phenol complexes 9.0g (0.99%) and making it evenly, on one side the liquid temperature is remained on 70 ℃, in 1 hour, slowly splash into dicyclopentadiene 150g on one side.After splashing into end, be warmed up to 140 ℃, restir 3 hours.
Ether type resultant content after mensuration splashes into is learnt, is 0.03.
Should illustrate that dicyclopentadiene etc. are measured in addition, confirm that water content is below 100ppm.In addition, also the water content of assaying reaction system aptly confirms that this water content is below 100ppm.
After reaction finishes, stop to stir, reaction solution is warming up to 210 ℃, underpressure distillation concentrates, and reclaims unreacted phenol, and reaction is finished, and obtains hydrocarbon-phenol resin 319g.
The softening temperature of the hydrocarbon-phenol resin that obtains is 87.0 ℃, and the phenolic hydroxyl group equivalent is 178.
Adopt
13The O/P ratio that C-NMR measures is 1.3, and ether type resultant containing ratio is below 0.02.
In addition, measure the absorbancy of resin solution and learn that the absorbancy of 350nm is 1.873, Gardner's chromatic number is more than 18.
The results are shown in the table 1.
Comparative example 2
(manufacturing of Resins, epoxy-3)
In 3 liters of 4 mouthfuls of flasks that have stirrer, reflux exchanger and thermometer, add the hydrocarbon-phenol resin 178g and the epoxy chloropropane 400g of the method manufacturing of adopting comparative example 1, make its dissolving then, stir, pressure in the reaction system is adjusted to 200hPa, is warming up to 68 ℃.Adding concentration continuously in this system on one side is the aqueous sodium hydroxide solution 100g of 48 quality %, Yi Bian carry out 3.5 hours reaction.The water that reaction generates and the water of aqueous sodium hydroxide solution as water-epoxy chloropropane azeotropic mixture, are discharged to outside the reaction system continuously by refluxing.Reaction makes reaction system return normal pressure after finishing, and is warmed up to 110 ℃, removes the water of reaction system fully.Superfluous epoxy chloropropane is removed in distillation under normal pressure, under the decompression of 20hPa, distills under 140 ℃ again.
In the mixture of resin that generates and sodium-chlor, add the aqueous sodium hydroxide solution 36g of methyl iso-butyl ketone (MIBK) 300g and 10 quality %, under 85 ℃, carry out 1.5 hours reaction.After reaction finishes, add methyl iso-butyl ketone (MIBK) 750g and water 300g, separatory removes the sodium chloride aqueous solution of sub-cloud.Then, add 150g water in the methyl iso-butyl ketone (MIBK) liquid layer, washing with the phosphoric acid neutralization, behind the separation water layer, is used the 800g water washing again, separates water layer.The separation property of oil reservoir and water layer is good, reclaims inorganic salt quantitatively.Distillation methyl iso-butyl ketone (MIBK) liquid layer under normal pressure then carries out underpressure distillation under 6.7hPa, 140 ℃, obtain 220g Resins, epoxy.The epoxy equivalent (weight) of this Resins, epoxy is 280.In addition, adopt the content of the simple function body of GPC method mensuration to be about 0.6 quality %.
In addition, measure the absorbancy of 2% dioxane solution of resin and learn that the absorbancy of 350nm is 1.793, Gardner's chromatic number is more than 18.
The results are shown in the table 1.
Comparative example 3
(manufacturing of hydrocarbon-phenol resin-4)
Add phenol and toluene in reactor, be heated to 160 ℃, make toluene and water azeotropic, toluene is removed in distillation simultaneously.Phenol amount in the system after the dehydration is 750g.Then, after adding 98% sulfuric acid 5.6g and making it evenly, on one side the liquid temperature is remained on 90～100 ℃, in 1 hour, slowly splash into dicyclopentadiene 150g on one side.After splashing into end, be warming up to 110 ℃, restir 3 hours.
Ether type resultant content after mensuration splashes into is learnt, is 0.04.
After reaction finishes, stop to stir, in reaction system, add hydrotalcite (trade(brand)name: 32g キ ョ-ワ-De 1000), stirred 30 minutes, make catalyst deactivation after, filtering reacting liquid.The filtrate decompression distillation that obtains is concentrated, obtain hydrocarbon-phenol resin 321g.
The softening temperature of the hydrocarbon-phenol resin that obtains is 96.0 ℃, and phenolic hydroxyl group is 169.
Adopt
13The O/P ratio that C-NMR measures is 1.3, and ether type resultant content is 0.02.
In addition, measure the absorbancy of resin solution and learn that the absorbancy of 350nm is 1.648, Gardner's chromatic number is more than 18.
The results are shown in the table 1.
Comparative example 4
(manufacturing of Resins, epoxy-4)
In 3 liters of 4 mouthfuls of flasks that have stirrer, reflux exchanger and thermometer, add the hydrocarbon-phenol resin 169g and the epoxy chloropropane 400g of the method manufacturing of adopting comparative example 3, make its dissolving then, stir, pressure in the reaction system is adjusted to 200hPa, is warming up to 68 ℃.Adding concentration continuously in this system on one side is the aqueous sodium hydroxide solution 100g of 48 quality %, Yi Bian carry out 3.5 hours reaction.The water that reaction generates and the water of aqueous sodium hydroxide solution as water-epoxy chloropropane azeotropic mixture, are discharged to outside the reaction system continuously by refluxing.Reaction makes reaction system return normal pressure after finishing, and is warmed up to 110 ℃, removes the water of reaction system fully.Superfluous epoxy chloropropane is removed in distillation under normal pressure, under the decompression of 20hPa, distills under 140 ℃ again.
In the mixture of resin that generates and sodium-chlor, add the aqueous sodium hydroxide solution 36g of methyl iso-butyl ketone (MIBK) 300g and 10 quality %, under 85 ℃, carry out 1.5 hours reaction.After reaction finishes, add methyl iso-butyl ketone (MIBK) 750g and water 300g, separatory removes the sodium chloride aqueous solution of sub-cloud.Then, add 150g water in the methyl iso-butyl ketone (MIBK) liquid layer, washing with the phosphoric acid neutralization, behind the separation water layer, is used the 800g water washing again, separates water layer.Oil reservoir is good with separating of water layer, reclaims inorganic salt quantitatively.Distillation methyl iso-butyl ketone (MIBK) liquid layer under normal pressure then carries out underpressure distillation under 6.7hPa, 140 ℃, obtain 220g Resins, epoxy.The epoxy equivalent (weight) of this Resins, epoxy is 258.In addition, the content of the simple function body of employing GPC method mensuration is below 0.1 quality %.
In addition, measure the absorbancy of 2% dioxane solution of resin and learn that the absorbancy of 350nm is 1.691, Gardner's chromatic number is more than 18.
The results are shown in the table 1.
The rerum natura of table 1 resin
| Ether type resultant content (molar percentage) | Softening temperature (℃) | Hydroxyl or epoxy equivalent (weight) (1) (g/eq) | O/P is than (mol ratio) | Absorbancy [350nm] | Gardner's chromatic number | |
| Hydrocarbon-phenol resin | ||||||
| Embodiment 1 | 0.43 | 96.0 | 170 | 2.7 | 0.983 | 14～15 |
| Embodiment 3 | 0.31 | 90.0 | 169 | 2.6 | 0.851 | 13～14 |
| Comparative example 1 | 0.03 | 87.0 | 178 | 1.3 | 1.873 | More than 18 |
| Comparative example 3 | 0.04 | 96.0 | 169 | 1.3 | 1.648 | More than 18 |
| Resins, epoxy | ||||||
| Embodiment 2 | - | - | 261 | - | 0.741 | 14～15 |
| Embodiment 4 | - | - | 256 | - | 0.710 | 11～12 |
| Comparative example 2 | - | - | 280 | - | 1.793 | More than 18 |
| Comparative example 4 | - | - | 258 | - | 1.691 | More than 18 |
Annotate (1): expression hydroxyl equivalent for hydrocarbon-phenol resin, expression epoxy equivalent (weight) for Resins, epoxy.
Utilize possibility on the industry
If employing the present invention, because reaction efficiency is high, can obtain at short notice the purpose product, further, the hydrocarbon-phenol resin that obtains except have with the past resin-phase with moisture-proof, heat resistance and resistance to cracking, also have the good features such as excellent color tone, article shaped outward appearance and mark.
In addition, the hydrocarbon-phenol resin glycidyl that said method is obtained and the epoxy resin that obtains, because moisture-proof and electrical characteristics are very good, use the moisture-proof of the solidfied material that this epoxy resin obtains also good, particularly useful on the purposes such as semiconductor resin, printed wiring board laminate, powdery paints, brake block, and because excellent color tone, molded appearance and mark etc. are good.
Claims (5)
1. the manufacture method of a hydrocarbon-phenol resin, it is characterized in that, the operation of employing comprises following (1) and (2), in the presence of acid catalyst, the acid catalyst concentration in the reaction solution is that 0.001～10 quality % and water content are carried out phenolic compound and the reaction with unsaturated cyclic hydrocarbon of 2 above carbon-to-carbon double bonds under the condition below the 200ppm:
(1) in the temperature range of the comparatively high temps to 90 from the fusing point of phenolic compound and 50 ℃ ℃, make its reaction on one side by on one side in phenolic compound, adding unsaturated cyclic hydrocarbon one by one or continuously with 2 above carbon-to-carbon double bonds, make ether type resultant in resultant of reaction shared molar percentage in the operation more than 0.1;
(2) after the interpolation of above-mentioned unsaturated cyclic hydrocarbon finishes, temperature is brought up to more than 110 ℃, reacted, the operation that the middle ether type resultant that generates of operation (1) is in fact eliminated by making it again.
2. the manufacture method of the hydrocarbon-phenol resin described in the claim 1 is characterized in that, in the above-mentioned hydrocarbon-phenol resin, about unsaturated cyclic hydrocarbon the position of substitution with respect to phenolic hydroxyl group in phenolic compound, the substitute proportion of ortho position/contraposition is more than 2.0.
3. the manufacture method of the hydrocarbon-phenol resin described in the claim 1 is characterized in that, after above-mentioned reaction finishes, reclaims unreacted phenolic compound after making catalyst deactivation.
4. the manufacture method of the hydrocarbon-phenol resin described in the claim 1 is characterized in that, above-mentioned phenolic compound is a phenol, and the unsaturated cyclic hydrocarbon with 2 above carbon-to-carbon double bonds is a dicyclopentadiene.
5. the manufacture method of a Resins, epoxy is characterized in that, in the presence of alkaline catalysts, the hydrocarbon-phenol resin that adopts the manufacture method described in the claim 1 to obtain is reacted with epoxyhalopropane after, remove catalyst residue, remove unreacted epoxyhalopropane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12376999 | 1999-04-30 | ||
| JP123769/1999 | 1999-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1302310A CN1302310A (en) | 2001-07-04 |
| CN1219804C true CN1219804C (en) | 2005-09-21 |
Family
ID=14868836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008007306A Expired - Lifetime CN1219804C (en) | 1999-04-30 | 2000-04-28 | Processes for producing hydrocarbon/phenol resin and producing epoxy resin |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7060779B1 (en) |
| JP (1) | JP3862958B2 (en) |
| KR (1) | KR100646210B1 (en) |
| CN (1) | CN1219804C (en) |
| TW (1) | TW527372B (en) |
| WO (1) | WO2000066645A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003137975A (en) * | 2001-11-02 | 2003-05-14 | Nippon Petrochemicals Co Ltd | Method for producing phenol resin and epoxy resin |
| JP3955199B2 (en) * | 2001-11-02 | 2007-08-08 | 新日本石油株式会社 | Phenol resin, epoxy resin, production method thereof, and resin composition for semiconductor encapsulant |
| US20080286579A1 (en) * | 2007-05-16 | 2008-11-20 | Boulder Based Designs Inc. | Method for identification of equipment |
| CN116261573B (en) * | 2021-10-06 | 2024-03-22 | 杰富意化学株式会社 | Process for producing triphenolmethane |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4927905A (en) * | 1988-11-14 | 1990-05-22 | The Dow Chemical Company | Process for the production of aromatic hydroxyl-containing compound-hydrocarbon resins |
| JP3090991B2 (en) | 1990-10-31 | 2000-09-25 | 三井化学株式会社 | Method for producing phenolic polymer |
| JPH04300816A (en) | 1991-03-27 | 1992-10-23 | Shiseido Co Ltd | Composition for oral cavity |
| JP2816774B2 (en) | 1991-03-29 | 1998-10-27 | 日本石油株式会社 | Phenolic resin, method for producing the resin, and epoxy resin composition for sealing material |
| JP3028385B2 (en) | 1992-01-31 | 2000-04-04 | 日石三菱株式会社 | Method for producing phenolic resin |
| US5368977A (en) * | 1992-03-23 | 1994-11-29 | Nippon Oil Co. Ltd. | Positive type photosensitive quinone diazide phenolic resin composition |
| JP3468308B2 (en) | 1994-03-16 | 2003-11-17 | 大日本インキ化学工業株式会社 | Method for producing phenolic resin and method for producing epoxy resin |
| JPH0853539A (en) | 1994-08-12 | 1996-02-27 | Dainippon Ink & Chem Inc | Production of phenol resin and epoxy resin |
| JPH0959344A (en) * | 1995-08-28 | 1997-03-04 | Dainippon Ink & Chem Inc | Epoxy resin composition and semiconductor sealing material |
| JP3332332B2 (en) | 1997-08-07 | 2002-10-07 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| JP4004617B2 (en) | 1997-12-29 | 2007-11-07 | 新日本石油株式会社 | Method for producing high purity hydrocarbon-phenolic resin |
| JPH11199659A (en) | 1997-12-29 | 1999-07-27 | Nippon Petrochem Co Ltd | Production of hydrocarbon-phenol resin having high purity |
| JP3866922B2 (en) * | 1998-12-15 | 2007-01-10 | 新日本石油化学株式会社 | Method for producing phenolic resin |
| US6291723B1 (en) * | 1999-09-02 | 2001-09-18 | Borden Chemical, Inc. | Diolefin/hydroxyaryl condensates and catalyst therefor |
-
2000
- 2000-04-28 WO PCT/JP2000/002818 patent/WO2000066645A1/en active IP Right Grant
- 2000-04-28 JP JP2000615672A patent/JP3862958B2/en not_active Expired - Lifetime
- 2000-04-28 CN CNB008007306A patent/CN1219804C/en not_active Expired - Lifetime
- 2000-04-28 TW TW089108169A patent/TW527372B/en not_active IP Right Cessation
- 2000-04-28 KR KR1020007014497A patent/KR100646210B1/en active IP Right Grant
- 2000-04-28 US US09/720,623 patent/US7060779B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR100646210B1 (en) | 2006-11-17 |
| TW527372B (en) | 2003-04-11 |
| WO2000066645A1 (en) | 2000-11-09 |
| JP3862958B2 (en) | 2006-12-27 |
| US7060779B1 (en) | 2006-06-13 |
| KR20010071545A (en) | 2001-07-28 |
| CN1302310A (en) | 2001-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1113076C (en) | Polyorganosiloxane simultaneously contg sulfoacid group and alkyl group with mercapto | |
| CN1160392C (en) | Phenolic resin, epoxy resin, and processes for producing these | |
| US7268192B2 (en) | Process for producing high-purity epoxy resin and epoxy resin composition | |
| CN1145353A (en) | Epoxy resin, resin composition, and resin-encapsulated semiconductor device | |
| CN1219804C (en) | Processes for producing hydrocarbon/phenol resin and producing epoxy resin | |
| CN1315734A (en) | Insulative material for printed circuit board | |
| CN1205245C (en) | Epoxy resins, process for production thereof, epoxy resin compositions and crured articles | |
| CN1249118C (en) | Phenolic resin, epoxy resin, processes for production thereof and epoxy resin composition | |
| CN1156504C (en) | Process for producing phenol-dicarbonyl condensates with increased fluorescence, epoxy resins, epoxy resin systems and laminates made with the same | |
| KR20230112112A (en) | Polycarbonate resin decomposition method, bisphenol production method, dialkyl carbonate production method, alkylaryl carbonate production method, diaryl carbonate production method, regenerated polycarbonate resin production method, epoxy resin production method, and epoxy resin cured product production method | |
| CN1211336C (en) | High-quality bisphenol A and process for producing the same | |
| JPH11255868A (en) | Preparation of phenol aralkyl resin | |
| JP3866922B2 (en) | Method for producing phenolic resin | |
| CN116261573B (en) | Process for producing triphenolmethane | |
| CN113574042B (en) | Bisphenol composition and polycarbonate resin | |
| CN1117782C (en) | Method of producing epoxy resin | |
| JP3721319B2 (en) | Method for producing phenolic resin and epoxy resin | |
| JPH11279265A (en) | Production of phenolic resin | |
| JP3955199B2 (en) | Phenol resin, epoxy resin, production method thereof, and resin composition for semiconductor encapsulant | |
| JP2003171439A (en) | Alicyclic epoxy compound and sealing material for light- emitting diode | |
| JPH11130836A (en) | Production high-purity epoxy resin | |
| CN116583495A (en) | Method for decomposing polycarbonate resin, method for producing bisphenol, method for producing dialkyl carbonate, method for producing alkylaryl carbonate, method for producing diaryl carbonate, method for producing recycled polycarbonate resin, method for producing epoxy resin, and method for producing cured epoxy resin | |
| TW202116846A (en) | Epoxy resin composition, cured product and electrical/electronic component | |
| CN1468878A (en) | Phenolic aldehyde resin and producing process thereof | |
| JPH04170423A (en) | Production of phenol polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: DIC CO., LTD. Free format text: FORMER OWNER: NIPPON PETROCHEMICALS CO., LTD. Effective date: 20100406 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20100406 Address after: Tokyo, Japan Patentee after: Dainippon Ink Chemicals Address before: Tokyo, Japan Patentee before: Nippon Petrochemicals Co., Ltd. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050921 |